Certain 3-oxy-2-pyridyl sulfonamide intermediates

ABSTRACT

N-pyridinesulfonyl-N&#39;-pyrimidinyl- and -triazinyl-ureas of formula I ##STR1## wherein R 1  is hydrogen or fluorine; 
     or R 1  together with R 3  is a C 2  -C 4  alkylene chain; 
     R 3  is hydrogen, fluorine or C 1  -C 3  alkyl; 
     R 2  is hydrogen, fluorine or C 1  -C 3  alkyl; 
     R 4  is hydrogen, fluorine, chlorine or C 1  -C 3  alkyl; 
     R 5  is hydrogen, fluorine, chlorine, C 1  -C 3  alkyl, or C 1  -C 3  alkyl substituted by fluorine or chlorine; 
     R a  is hydrogen or halogen, or a C 1  -C 4  alkyl, C 1  -C 4  alkoxy or C 1  -C 4  alkylthio radical each of which may be unsubstituted or mono- or poly-substituted by halogen; 
     R b  is hydrogen or a C 1  -C 4  alkyl radical; 
     X is C 1  -C 3  alkyl, C 1  -C 3  alkyl mono- to tri-substituted by halogen, C 1  -C 3  alkoxy, or C 1  -C 3  alkoxy mono- to tri-substituted by halogen; 
     Y is halogen, C 1  -C 3  alkyl, C 1  -C 3  alkyl mono- to tri-substituted by halogen, C 1  -C 3  alkoxy, or C 1  -C 3  alkoxy mono- to tri-substituted by halogen, or is cyclopropyl, methylamino or dimethylamino; and 
     E is nitrogen or the methine group, 
     and the salts of those compounds, with the proviso that at least one of the radicals R 1  to R 5  is fluorine, or one of the radicals R 4  and R 5  is chlorine, have good selective-herbicidal properties. The preparation of those compounds and their use as herbicidal active ingredients is described.

This is a division of Ser. No. 08/369,063, filed Jan. 5, 1995,abandoned, which is a division of Ser. No. 08/224,393, filed Apr. 7,1994, now U.S. Pat. No. 5,403,814, which is a continuation of Ser. No.08/094,824, filed Jul. 20, 1993, abandoned, which is acontinuation-in-part of Ser. No. 07/938,036, 35 USC 37 1 date Nov. 12,1992, abandoned, which is a national stage of PCT/EP92/00555, filed Mar.13, 1992.

The present invention relates to novel herbicidally active andplant-growth-regulating N-pyridinesulfonyl-N'-pyrimidinyl- and-triazinyl-ureas, to processes for the preparation thereof, tocompositions comprising them as active ingredients, and to the usethereof for controlling weeds, especially selectively in crops of usefulplants, or for regulating and inhibiting plant growth.

Urea compounds, triazine compounds and pyrimidine compounds havingherbicidal action are generally known. For example European Patent No.103 543 and U.S. Pat. No. 4,544,401 describe herbicidally active andplant-growth-regulating N-pyridinesulfonyl-N'-pyrimidinyl- and-triazinyl-ureas. The compounds disclosed therein are not, however,always able to satisfy requirements in respect of potency andselectivity. There is accordingly a need for compounds that haveimproved activity and are more selective.

Novel sulfonylureas having improved herbicidal andplant-growth-regulating properties have now been found.

The N-pyridinesulfonyl-N'-pyrimidinyl- and -triazinyl-ureas according tothe invention correspond to formula I ##STR2## wherein R₁ is hydrogen orfluorine;

or R₁ together with R₃ is a C₂ -C₄ alkylene chain;

R₃ is hydrogen, fluorine or C₁ -C₃ alkyl;

R₂ is hydrogen, fluorine or C₁ -C₃ alkyl;

R₄ is hydrogen, fluorine, chlorine or C₁ -C₃ alkyl;

R₅ is hydrogen, fluorine, chlorine, C₁ -C₃ alkyl, or C₁ -C₃ alkylsubstituted by fluorine or chlorine;

R_(a) is hydrogen or halogen, or a C₁ -C₄ alkyl, C₁ -C₄ alkoxy or C₁ -C₄alkylthio radical each of which may be unsubstituted or mono- orpoly-substituted by halogen;

R_(b) is hydrogen or a C₁ -C₄ alkyl radical;

X is C₁ -C₃ alkyl, C₁ -C₃ alkyl mono- to tri-substituted by halogen, C₁-C₃ alkoxy, or C₁ -C₃ alkoxy mono- to tri-substituted by halogen;

Y is halogen, C₁ -C₃ alkyl, C₁ -C₃ alkyl mono- to tri-substituted byhalogen, C₁ -C₃ alkoxy, or C₁ -C₃ alkoxy mono- to tri-substituted byhalogen, or is cyclopropyl, methylamino or dimethylamino; and

E is nitrogen or the methine group,

and the salts of those compounds, with the proviso that at least one ofthe radicals R₁ to R₅ is fluorine, or one of the radicals R₄ and R₅ ischlorine.

Suitable substituents R₂ to R₅ representing alkyl groups arestraight-chain or branched alkyl groups, for example methyl, ethyl,n-propyl and isopropyl.

The alkyl groups occurring as or in the substituent R_(a) includestraight-chain or branched alkyl groups, such as, for example, methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.Those alkyl groups may be mono- or poly-substituted by halogen, halogenbeing in particular fluorine, chlorine, bromine or iodine. Of thesealkyl groups mono- or poly-substituted by halogen preference is given tothose alkyl groups that are mono- to tri-substituted by halogen,especially fluorine or chlorine. Especially preferred alkyl groups mono-to tri-substituted by fluorine or chlorine are e.g. trifluoromethyl,1-fluoroethyl, 1,1-dichloroethyl, 3,3,3-trifluoropropyl,2-fluoroisopropyl and 3-fluoropropyl.

Alkyl groups mono- or poly-substituted by fluorine or chlorine presentas the substituent R₅ include straight-chain or branched alkyl groupsmono- to tri-substituted by fluorine or chlorine, e.g. dichloromethyl ortrifluoromethyl.

The C₁ -C₃ alkyl radicals present as or in the substituents X and Yinclude in particular methyl, ethyl, n-propyl and isopropyl, especiallymethyl or ethyl, and also the haloalkyls derived from those radicalsthat are mono- to tri-substituted by halogen. Of the C₁ -C₃ alkyl groupsmono- to tri-substituted by halogen present in the substituents X and Y,C₁ -C₃ alkyl groups that are mono- to tri-substituted by fluorine orchlorine are preferred. Especially preferred C₁ -C₃ alkyl groups mono-to tri-substituted by halogen present in the substituents X and Y are,for example, trifluoromethyl, difluoromethyl, 2-chloroethyl,chlorodifluoromethyl, dichloromethyl, chlorofluoromethyl,1,1-dichloroethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl or2,3-dichloropropyl, with fluoromethyl, chloromethyl, difluoromethyl andtrifluoromethyl being most especially preferred.

Alkylthio is, for example, methylthio, ethylthio, propylthio,isopropylthio, n-butylthio, iso-butylthio, sec-butylthio ortert-butylthio.

Alkoxy is, for example, methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy,isobutoxy, sec-butoxy or tert-butoxy; preferably methoxy or ethoxy.

There come into consideration as a C₂ -C₄ alkylene chain denoted by R₁and R₃ ethylene, propylene or butylene.

The invention also includes the salts that the compounds of formula Ican form with amines, alkali metal and alkaline earth metal bases orquaternary ammonium bases.

Of the alkali metal and alkaline earth metal hydroxides as salt-formers,prominence is to be given to the hydroxides of lithium, sodium,potassium, magnesium and calcium, but especially to the hydroxides ofsodium and potassium.

Examples of amines that are suitable for salt formation are primary,secondary and tertiary aliphatic and aromatic amines, such asmethylamine, ethylamine, propylamine, isopropylamine, the four isomersof butylamine, dimethylamine, diethylamine, diethanolamine,dipropylamine, diisopropylamine, di-n-butylamine, pyrrolidine,piperdine, morpholine, trimethylamine, triethylamine, tripropylamine,quinuclidine, pyridine, quinoline and isoquinoline, but especiallyethyl-, propyl-, diethyl- or triethyl-amine, and more especiallyisopropylamine and diethanolamine.

Examples of quaternary ammonium bases are generally the cations ofhaloammonium salts, for example the tetramethylammonium cation, thetrimethylbenzylammonium cation, the triethylbenzylammonium cation, thetetraethylammonium cation and the trimethylethylammonium cation, butalso the ammonium cation.

Preferred are compounds of formula I wherein R₁ and R₃, eachindependently of the other, are hydrogen or fluorine; R₂ is hydrogen,fluorine or C₁ -C₃ alkyl; R₄ is hydrogen, fluorine or chlorine; and R₅is hydrogen or fluorine, or C₁ -C₃ alkyl that is unsubstituted orsubstituted by fluorine or chlorine, and R_(a), R_(b), X, Y and E are asdefined for formula I, and the compoundsN-[3-(2,5-dichloro-2-methylpropoxy)-pyrid-2-yl-sulfonyl]-N'-(4,6-bis-difluoromethoxy-pyrimidin-2-yl)ureaandN-[3-(2,5-dichloro-2-methylpropoxy)-pyrid-2-yl-sulfonyl]-N'-(4,6-bis-difluoromethoxy-1,3,5-triazin-2-yl)urea.

Of the compounds of formula I and also of the preferred compounds offormula I those wherein R_(a) and R_(b) are each hydrogen are especiallypreferred.

Also especially preferred are compounds of formula I, including all ofthe above-mentioned preferred compounds, wherein the radical of formulaIa ##STR3## contains a maximum of 3 carbon atoms.

Most especially preferred are compounds of formula I, including all ofthe above-mentioned preferred compounds, wherein at least one of theradicals R₃, R₄ and R₅ in the radical of formula Ia is a halogen atom,i.e. R₃ is a fluorine atom, and each of R₄ and R₅, independently of theother, is a fluorine or a chlorine atom. In those compounds, the oxygenatom is separated from the halogen atom in the radical R₃, R₄ or R₅ by 2carbon atoms. Especially preferred among such compounds of formula Iaare those wherein only one of the radicals R₃, R₄ and R₅ is a halogenatom, i.e. R₃ is fluorine, R₄ is fluorine or chlorine, or R₅ is fluorineor chlorine. In those most especially preferred compounds of formula I,preferably R₁ is hydrogen and R₂ is hydrogen or C₁ -C₃ alkyl.

Important compounds of formula I, including all the above-mentionedpreferred compounds, are those wherein one of the radicals X and Y ismethyl, methoxy, ethoxy, difluoromethoxy or chlorine.

Most especially important are compounds of formula I, including all ofthe mentioned preferred compounds, wherein E is the methine bridge.

In the compounds of formula I, the radicals preferably have thefollowing meanings:

R₁ is hydrogen or fluorine;

R₂ is hydrogen, fluorine, methyl or ethyl;

R₃ is hydrogen, fluorine or methyl, or R₃ together with R₁ is a C₄alkylene chain;

R₄ is hydrogen, fluorine, chlorine, methyl or ethyl;

R₅ is hydrogen, fluorine, chlorine, trifluoromethyl or dichloromethyl;

R_(a) and R_(b) are each hydrogen;

X is methyl, methoxy, ethoxy, difluoromethoxy or 2,2,2-trifluoroethoxy;

Y is chlorine, methyl, cyclopropyl, methoxy, difluoromethoxy,methylamino or dimethylamino; and

E is nitrogen or the methine group.

The following compound may be mentioned as a preferred individualcompound from the scope of formula I:

N-[3-(2-chloroethoxy)-pyridine-2-sulfonyl]-N'-(4,6-dimethoxypyrimidin-2-yl)urea.

The compounds of formula I are prepared by reacting a3-haloalkoxy-pyrid-2-yl-sulfonamide of formula II ##STR4## whereinR_(a), R₁, R₂, R₃, R₄ and R₅ are as defined for formula I, with apyrimidinyl or triazinyl carbamate of formula III ##STR5## wherein X, Y,R_(b) and E are as defined for formula I and R₆ is phenyl that may besubstituted by C₁ -C₄ alkyl or by halogen, in an inert organic solventin the presence of a base.

According to another process for the preparation of the compound offormula Ia 3-alkoxy-pyridylsulfonamide of formula II in an inert solventor diluent is reacted with an isocyanate of formula IV ##STR6## whereinX, Y and E are as defined for formula I.

The N-pyridinesulfonyl-N'-pyrimidinyl- and -triazinyl-sulfonylureas offormula I are also prepared by reacting a pyridylsulfonamide of formulaV ##STR7## wherein R_(a), R₁, R₂, R₃, R₄ and R₅ are as defined forformula I and A is a radical ##STR8## wherein R₆ has the meaning given,or a radical O═C═N-, in the presence of a base with a 2-amino-pyrimidineor -triazine of formula Va ##STR9## wherein E, X and Y are as definedfor formula I.

The reactions to form compounds of formula I are advantageously carriedout in aprotic, inert organic solvents. Such solvents are hydrocarbons,such as benzene, toluene, xylene or cyclohexane, chlorinatedhydrocarbons, such as dichloromethane, trichloromethane,tetrachloromethane or chlorobenzene, ethers, such as diethyl ether,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,tetrahydrofuran or dioxane, nitriles, such as acetonitrile orpropionitrile, amides, such as dimethylformamide or diethylformamide, orN-methylpyrrolidone. The reaction temperatures are preferably from -20°to +120° C.

The reactions are generally slightly exothermic and can be carried outat room temperature. In order to reduce the reaction time or also toinitiate the reaction, it is expedient to heat the reaction mixture toboiling point briefly. The reaction times can also be reduced by addinga few drops of base as a reaction catalyst. Suitable bases areespecially tertiary amines, such as trimethylamine, triethylamine,quinuclidine, 1,4-diazabicyclo-[2.2.2]octane,1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene.Other bases that may be used, however, are inorganic bases, such ashydrides, e.g. sodium or calcium hybride, hydroxides, e.g. sodium andpotassium hydroxide, carbonates, e.g. sodium and potassium carbonate, orhydrogen carbonates, e.g. potassium and sodium hydrogen carbonate.

The end products of formula I can be isolated by concentration and/orevaporation of the solvent and can be purified by recrystallisation ortrituration of the solid residue in solvents in which they are notreadily soluble, such as ethers, aromatic hydrocarbons or chlorinatedhydrocarbons.

The intermediates of formulae IV and V are known or can be preparedanalogously to known processes. Processes for the preparation ofN-pyrimidinyl and N-triazinyl carbamates are described, for example, inEP-A-101 670.

N-Pyrimidinyl and N-triazinyl isocyanates can be prepared from thecorresponding 2-amino-pyrimidines and -triazines, respectively, offormula Va ##STR10## wherein X, Y and E are as defined for formula I.Such reactions and the preparation of compounds of formula Ill aredescribed in EP-A-044 808. Compounds of formula Va are known fromEP-A-070 804. The intermediates of formula II are novel and weredeveloped specifically for the synthesis of the compounds of formula I.The present invention therefore also relates to them.

The same preferences with respect to R_(a), R₁, R₂, R₃, R₄ and R₅ as forcompounds of formula I apply to the above intermediates.

The novel intermediates of formula II can be prepared by variousprocesses that are known per se. For example the compounds of formula IImay be obtained by reacting a 3-fluoropyrid-2-yl-sulfonamide of formulaVI ##STR11## wherein R_(a) is as defined for formula I, with an alkanolof formula VII ##STR12## wherein R₁ ' is hydrogen and R₂ ' is hydrogenor C₁ -C₃ alkyl, or R₁ ' together with R₃ is C₂ -C₄ alkylene, R₃ is asdefined for formula I and R₄ and R₅ are as defined for formula I but maynot be chlorine. Such reactions are described in Synth. Commun. 12(9),695 (1982) or in EP-A-103 543.

The compounds of formula II can also be prepared by reacting a3-fluoro-pyrid-2-ylsulfonamide of formula VI with an alkanol of formulaVIIa ##STR13## wherein R₁ ', R₂ ', R₃ and R₄ are as defined for formulaVII, R₅ ' is C₁ -C₃ alkylene, R₆ is benzyl or tert-butyl, and m is theinteger 0 or 1, and then removing the protecting group R₆ again, e.g. byhydrolysis in acidic or alkaline medium or by hydrogenation, inaccordance with the following synthesis scheme: ##STR14##

The removal of the tert-butyl protecting group in acidic medium iscarried out in accordance with J. Chem. Soc. 1963, 755. A benzylprotecting group is removed e.g. with hydrogen in the presence of acatalyst; see in this connection J. Am. Chem. Soc. 93, 1746 (1971). Thehydroxy group is then replaced by a chlorine atom according to a methoddescribed in EP-A-179 022, EP-A-327 504 or also in Adv. Org. Chem. 9(Part 1), 421. The hydroxy group can also be replaced by a fluorineatom, according to a process described in Organic Reactions 1983, 513.

The intermediates of formula II may also be prepared, for example,according to the following reaction scheme: ##STR15##

In these formulae, R_(a), R₁, R₂, R₃, R₄ and R₅ are as defined forformula I, whilst Z is a suitable leaving group, for example bromine ora tolylsulfonyloxy or methylsulfonyloxy group, and B is either alreadythe sulfonamido group or is an isopropylmercapto or benzylthio groupstill to be converted into the sulfonamido group, in which case it isconverted into the chlorosulfonyl radical which is then converted intothe sulfonamido group; see in that connection EP-A-103 543 or U.S. Pat.No. 4,522,645.

A close reaction variant for the preparation of compounds of formula IIawherein R₄ is hydrogen and R₅ is fluorine or chlorine is shown by thefollowing reaction scheme: ##STR16## wherein R_(a), B, Z, R₁ and R₂ havethe meanings given, R₃ ' is hydrogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy, R₃" is hydrogen or C₁ -C₃ alkyl, and R₁ together with R₃ ', and R₁together with R₃ ", is also a C₂ -C₄ alkylene chain. The reaction of thecompounds of formula IXa to form the compounds of formula IIa is carriedout according to a method described in EP-A-179 022, EP-A-327 504 oralso in Adv. Org. Chem. 9 (Part 1), 421. The hydroxy group may also bereplaced by a fluorine atom according to a process described in OrganicReactions 1983, 513.

Furthermore, the intermediates of formula II can also be prepared byreactions in accordance with the following scheme: ##STR17## In theseformulae R_(a) is as defined for formula I, B is the sulfonamido groupor an isopropylmercapto or benzylthio group that is to be convened intothe sulfonamido group, whilst A═A' is a di- or poly-haloalkene thatcorresponds in the number of carbon atoms and halogen atoms to theradical of formula Ia. These reactions are carded out e.g. analogouslyto the following literature sources:

EP-A-179 022;

EP-A-318 781;

EP-A-327 504;

L'actualite chimique, May 1987, 151;

J.Fluofine Chemistry 20, 759 (1982);

Ind. Eng. Chem. 39, 412 (1947);

J.Am. Chem. Soc. 82, 5116 (1960).

The starting compounds required for the preparation processes are eitherknown or can easily be prepared from known compounds.

The compounds of formula VI ##STR18## and their preparation aredescribed in EP-A-402 316. Starting materials of formula VIII ##STR19##are prepared from compounds of formula VI by replacing the fluorine atomby the radical of a reactive alkanol, for example benzyl alcohol,tert-butyl alcohol, the alkane radical assuming the role of a protectinggroup which is then removed again by hydrolysis or hydrogenolysis. Thesereactions are described e.g. in EP-A-103 543 and illustrated by thefollowing formula scheme: ##STR20## According to a method described inU.S. Pat. No. 4,522,645 the starting materials of formula VIII can alsobe prepared according to the scheme below: ##STR21## The compounds offormula I are generally used successfully at rates of application offrom 0.001 to 2 kg/ha, especially from 0.005 to 1 kg/ha. Theconcentration required to achieve the desired effect can be determinedby experiment. It is dependent on the type of action, the stage ofdevelopment of the cultivated plant and of the weed, and also on theapplication (place, time, method) and, in dependence on thoseparameters, can vary within wide limits.

When used at relatively low rates of application, the compounds offormula I are distinguished by growth-inhibiting and herbicidalproperties, which render them excellently suitable for use in crops ofuseful plants, especially in cereals, cotton, soybeans, rape, maize andrice, their use in maize crops being most especially preferred.

The invention relates also to herbicidal and plant-growth-regulatingcompositions comprising a novel compound of formula I, and to methods ofinhibiting plant growth.

Plant growth regulators are substances that bring about agronomicallydesirable biochemical and/or physiological and/or morphological changesin/to the plant.

The active ingredients incorporated in the compositions according to theinvention influence plant growth in different ways depending on the timeof application, the concentration, the type of application and theenvironmental conditions. Plant growth regulators of formula I can, forexample, inhibit the vegetative growth of plants. This type of action isvaluable in the case of lawn areas, in the cultivation of ornamentals,in fruit plantations, in the case of roadside embankments and in sportsfields and industrial sites, but also in the specific inhibition ofside-shoots, as in the case of tobacco. In agriculture, inhibition ofthe vegetative growth of cereals leads, owing to a strengthening of thestalk, to reduced lodging, and similar agronomic effects are achieved inrape, sunflowers, maize and other cultivated plants. Moreover, byinhibiting the vegetative growth it is possible to increase the numberof plants per unit area. Another field of use for growth inhibitors isthe selective control of cover plants in plantations or widely spacedcrops which is achieved by greatly inhibiting the growth of the covercrops without killing them, so that competition with the main crop iseliminated but the agronomically positive effects, such as erosionprevention, fixing of nitrogen and loose soil structure, are preserved.

A method of inhibiting plant growth is to be understood as being amethod of controlling a plant's natural development without changing itslife-cycle, as determined by genetic characteristics, in the sense ofmutation. The method of regulating growth is applied at a time in theplant's development that has to be determined for each individual case.The compounds of formula I can be applied pre- or post-emergence, forexample to the seeds or seedlings, to roots, tubers, stalks, leaves,blossoms or other pans of the plant. This can be done, for example, byapplying the compound as such or in the form of a composition to theplants, and/or by treating the plant's nutrient medium (soil).

Various methods and techniques are suitable for the use of the compoundsof formula I or of compositions containing them for regulating plantgrowth, for example the following:

i) Seed dressing

a) Dressing the seeds with an active ingredient formulated as a wettablepowder, by shaking in a container until the formulation is uniformlydistributed over the surface of the seeds (dry dressing). Up to 4 g ofcompound of formula I (in the case of a 50% formulation: up to 8.0 g ofwettable powder) are used per 1 kg of seed.

b) Dressing the seeds with an emulsifiable concentrate of the activeingredient, or with an aqueous solution of the compound of formula Iformulated as a wettable powder, according to method a) (wet dressing).

c) Dressing by soaking the seeds for a period of from 1 to 72 hours in aliquor containing up to 1000 ppm of compound of formula I and, ifdesired, subsequently drying the seeds (seed soaking).

Seed dressing or treatment of the germinated seedling are naturally thepreferred methods of application because the treatment with the activeingredient is directed wholly at the target crop. From 0.001 g to 4.0 gof active ingredient are normally used per 1 kg of seed, although,depending on the method employed, which also allows the addition ofother active ingredients or micronutrients, amounts that exceed or fallshort of the specified concentration limits may be employed (repeatdressing).

ii) Controlled release of active ingredient

A solution of ate active ingredient is applied to mineral granulatedcarders or polymerised granules (urea/formaldehyde) and allowed to dry.If required, a coating may be applied (coated granules), which allowsthe active ingredient to be released in metered amounts over a specificperiod of time.

The compounds of formula I are used in unmodified form, as obtainablefrom synthesis, or, preferably, as compositions together with theadjuvants conventionally employed in formulation technology, and aretherefore formulated in known manner e.g. into emulsifiableconcentrates, directly sprayable or dilutable solutions, diluteemulsions, wettable powders, soluble powders, dusts, granules, and alsoencapsulations in e.g. polymer substances. As with the nature of thecompositions, the methods of application, such as spraying, atomising,dusting, wetting, scattering or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixturescomprising the compound (active ingredient) of formula I and, whereappropriate, one or more solid or liquid adjuvants, are prepared inknown manner, e.g. by homogeneously mixing and/or grinding the activeingredients with extenders, e.g. solvents, solid carriers and, whereappropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionscontaining 8 to 12 carbon atoms, such as mixtures of alkylbenzenes, e.g.xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatichydrocarbons such as paraffins, cyclohexane or tetrahydronaphthalene;alcohols such as ethanol, propanol or butanol; glycols and their ethersand esters, such as propylene glycol or dipropylene glycol ether,ketones such as cyclohexanone, isophorone or diacetone alcohol, stronglypolar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide orwater; vegetable oils and their esters, such as rape oil, castor oil orsoybean oil; and, where appropriate, also silicone oils.

The solid carriers used, e.g. for dusts and dispersible powders, arenormally natural mineral fillers such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties it is also possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarders are porous types, for example pumice, broken brick, sepiolite orbentonite; and suitable nonsorbent carriers are, for example, calcite orsand. In addition, a great number of pregranulated materials ofinorganic or organic nature can be used, e.g. especially dolomite orpulverised plant residues.

Depending on the nature of the compound of formula I to be formulated,suitable surface-active compounds are non-ionic, cationic and/or anionicsurfactants having good emulsifying, dispersing and wetting properties.The term "surfactants" will also be understood as comprising mixtures ofsurfactants.

Both so-called water-soluble soaps and water-soluble syntheticsurface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts orunsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, orof natural fatty acid mixtures which can be obtained e.g. from coconutoil or tallow oil. Mention may also be made of fatty acid methyltaurinsalts.

More frequently, however, so-called synthetic surfactants are used,especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonatedbenzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are usually in the form ofalkali metal salts, alkaline earth metal salts or unsubstituted orsubstituted ammonium salts and contain a C₈ -C₂₂ alkyl radical, whichalso includes the alkyl moiety of acyl radicals, e.g. the sodium orcalcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixtureof fatty alcohol sulfates obtained from natural fatty acids. Thesecompounds also comprise the salts of sulfated and sulfonated fattyalcohol/ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and one fatty acid radicalcontaining 8 to 22 carbon atoms. Examples of alkylarylsulfonates are thesodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid,dibutylnaphthalenesulfonic acid, or of a condensate ofnaphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoricacid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethyleneoxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives ofaliphatic or cycloaliphatic alcohols, saturated or unsaturated fattyacids and alkylphenols, said derivatives containing 3 to 30 glycol ethergroups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moietyand 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts ofpolyethylene oxide with polypropylene glycol,ethylendiaminopolypropylene glycol and alkylpolypropylene glycolcontaining 1 to 10 carbon atoms in the alkyl chain, which adductscontain 20 to 250 ethylene glycol ether groups and 10 to 100 propyleneglycol ether groups. These compounds usually contain 1 to 5 ethyleneglycol units per propylene glycol unit.

Representative examples of non-ionic surfactants arenonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethylene oxide adducts,tributylphenoxypolyethoxyethanol, polyethylene glycol acidoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylenesorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts whichcontain, as N-substituent, at least one C₈ -C₂₂ alkyl radical and, asfurther substituents, unsubstituted or halogenated lower alkyl, benzylor hydroxy-lower alkyl radicals. The salts are preferably in the form ofhalides, methyl sulfates or ethyl sulfates, e.g.stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in formulation technology aredescribed inter alia in the following publications:

"Mc Cutcheon's Detergents and Emulsifiers Annual", McPublishing Corp.,Glen Rock, New Jersey, 1988.

M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, ChemicalPublishing Co., New York, 1980-1981.

Dr. Helmut Stache "Tensid-Taschenbuch", Carl Hanser Verlag,Munich/Vienna 1981.

The herbicidal and plant-growth-regulating compositions generallycomprise 0.1 to 99%, preferably 0.1 to 95%, of a compound of formula I,1 to 99% of a solid or liquid adjuvant and 0 to 25%, preferably 0.1 to25%, of a surfactant.

Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further additives such asstabilisers, for example vegetable oils rand epoxidised vegetable oils(epoxidised coconut oil, rape oil or soybean oil), antifoams, forexample silicone oil, preservatives, viscosity regulators, binders,tackifiers as well as fertilisers or other active ingredients forobtaining special effects.

Preferred formulations are composed in particular of the followingconstituents (throughout, percentages are by weight):

    ______________________________________                                        Emulsifiable concentrates:                                                    active ingredient:                                                                           1 to 90%, preferably 5 to 20%                                  surfactant:    1 to 30%, preferably 10 to 20%                                 liquid carrier:                                                                              5 to 94%, preferably 70 to 85%                                 Dusts:                                                                        active ingredient:                                                                           0.1 to 10%, preferably 0.1 to 1%                               solid carrier: 99.9 to 90%, preferably 99.9 to 99%                            Suspension concentrates:                                                      active ingredient:                                                                           5 to 75%, preferably 10 to 50%                                 water:         94 to 24%, preferably 88 to 30%                                surfactant:    1 to 40%, preferably 2 to 30%                                  Wettable powders:                                                             active ingredient:                                                                           0.5 to 90%, preferably 1 to 80%                                surfactant:    0.5 to 20%, preferably 1 to 15%                                solid carrier: 5 to 95%, preferably 15 to 90%                                 Granules:                                                                     active ingredient:                                                                           0.5 to 30%, preferably 3 to 15%                                solid carrier: 99.5 to 70%, preferably 97 to 85%                              ______________________________________                                    

Formulation Examples for liquid active ingredients of formula I(throughout, percentages are by weight)

    ______________________________________                                        1. Emulsifiable concentrates                                                                        a)     b)       c)                                      ______________________________________                                        a compound of Table 1 25%    40%      50%                                     calcium dodecylbenzenesulfonate                                                                      5%     8%       6%                                     castor oil polyethylene glycol                                                                       5%    --       --                                      ether (36 mol of ethylene oxide)                                              tributylphenol polyethylene glycol                                                                  --     12%       4%                                     ether (30 mol of ethylene oxide)                                              cyclohexanone         --     15%      20%                                     xylene mixture        65%    25%      20%                                     ______________________________________                                    

Emulsions of may desired concentration can be produced from suchconcentrates by dilution with water.

    ______________________________________                                        2. Solutions     a)     b)      c)     d)                                     ______________________________________                                        a compound of Table 1                                                                          80%    10%     5%     95%                                    propylene glycol monomethyl                                                                    20%    --      --     --                                     ether                                                                         polyethylene glycol                                                                            --     70%     --     --                                     (mol. wt. 400)                                                                N-methyl-2-pyrrolidone                                                                         --     20%     --     --                                     epoxidised coconut oil                                                                         --     --      1%      5%                                    petroleum fraction (boiling                                                                    --     --      94%    --                                     range 160-190° C.)                                                     ______________________________________                                    

These solutions are suitable for application in the form of micro-drops.

    ______________________________________                                        3. Granules     a)       b)      c)    d)                                     ______________________________________                                        a compound of Table 1                                                                         5%       10%      8%   21%                                    kaolin          94%      --      79%   54%                                    highly dispersed silicic acid                                                                 1%       --      13%    7%                                    attapulgite     --       90%     --    18%                                    ______________________________________                                    

The active ingredient is dissolved in methylene chloride, the solutionis sprayed onto the carrier, and the solvent is subsequently evaporatedoff in vacuo.

    ______________________________________                                        4. Dusts            a)      b)                                                ______________________________________                                        a compound of Table 1                                                                             2%      5%                                                highly dispersed silicic acid                                                                     1%      5%                                                talcum              97%     --                                                kaolin              --      90%                                               ______________________________________                                    

Ready-for-use dusts are obtained by homogeneously mixing the carrierswith the active ingredient.

Formulation Examples for solid active ingredients of formula I(throughout, percentages are by weight)

    ______________________________________                                        5. Wettable powders a)       b)     c)                                        ______________________________________                                        a compound of Table 1                                                                             25%      50%    75%                                       sodium lignosulfonate                                                                              5%       5%    --                                        sodium laurylsulfate                                                                               3%      --      5%                                       sodium diisobutylnaphthalene-                                                                     --        6%    10%                                       sulfonate                                                                     octylphenol polyethylene glycol                                                                   --        2%    --                                        ether (7-8 mol of ethylene oxide)                                             highly dispersed silicic acid                                                                      5%      10%    10%                                       kaolin              62%      27%    --                                        ______________________________________                                    

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders which can be diluted with water to give suspensions of thedesired concentration.

    ______________________________________                                        6. Emulsifiable concentrate                                                   ______________________________________                                        a compound of Table 1 10%                                                     octylphenol polyethylene glycol                                                                      3%                                                     ether (4-5 mol of ethylene oxide)                                             calcium dodecylbenzenesulfonate                                                                      3%                                                     castor oil polyglycol ether                                                                          4%                                                     (36 mol of ethylene oxide)                                                    cyclohexanone         30%                                                     xylene mixture        50%                                                     ______________________________________                                    

Emulsions of arty required concentration can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        7. Dusts             a)     b)                                                ______________________________________                                        a compound of Table 1                                                                               5%     8%                                               talcum               95%    --                                                kaolin               --     92%                                               ______________________________________                                    

Ready-for-use dusts are obtained by mixing the active ingredient withthe carriers and grinding the mixture in a suitable mill.

    ______________________________________                                        8. Extruder granules                                                          ______________________________________                                        a compound of Table 1                                                                            10%                                                        sodium lignosulfonate                                                                             2%                                                        carboxymethylcellulose                                                                            1%                                                        kaolin             87%                                                        ______________________________________                                    

The active ingredient is mixed and ground with the adjuvants, and themixture is subsequently moistened with water. The mixture is extrudedand then dried in a stream of air.

    ______________________________________                                        9. Coated granules                                                            ______________________________________                                        a compound of Table 1 3%                                                      polyethylene glycol (mol. wt. 200)                                                                  3%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

    ______________________________________                                        10. Suspension concentrate                                                    ______________________________________                                        a compound of Table 1 40%                                                     propylene glycol      10%                                                     nonylphenol polyethylene glycol                                                                      6%                                                     ether (15 mol of ethylene oxide)                                              sodium lignosulfonate 10%                                                     carboxymethylcellulose                                                                               1%                                                     silicone oil in the form of a 75%                                                                    1%                                                     aqueous emulsion                                                              water                 32%                                                     ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired concentration can be obtained by dilution with water. Thecompounds of formula I are used in unmodified form or, preferably, ascompositions together with the adjuvants conventionally employed informulation technology, and are therefore formulated in known mannere.g. into emulsifiable concentrates, directly sprayable or dilutablesolutions, dilute emulsions, wettable powders, soluble powders, dusts,granules, and also encapsulations in e.g. polymer substances. As withthe nature of the compositions, the methods of application, such asspraying, atomising, dusting, scattering or pouring, are chosen inaccordance with the intended objectives and the prevailingcircumstances.

PREPARATION EXAMPLES Example P1: Preparation of3-hydroxy-pyrid-2-ylsulfonamide (intermediate) ##STR22##

A solution of 263.7 g of 3-benzyloxy-pyrid-2-ylsulfonamide in 2.5 ofmethanol is hydrogenated with the addition of 26 g of 5% Pd/C catalyst.After 23.8 of hydrogen have been absorbed, the catalyst is filtered off.After evaporation of the methanol, 3-hydroxypyrid-2-ylsulfonamideremains in the form of a crystalline mass. Melting point 162°-164° C.

Example P2: Preparation of 3-(2-chloroethoxy)-pyrid-2-ylsulfonamide(intermediate) ##STR23##

First 17.9 g of potassium carbonate and then 28.14 g of2-(2-chloroethyl)-toluene-4-sulfonate are added, with stirring, to asolution of 17.4 g of 3-hydroxy-pyrid-2-ylsulfonamide in 240 ml ofdimethylacetamide. The reaction mixture is stirred for 1.5 hours at 80°C. and then cooled and filtered. The filtration residue is washed withacetonitrile. The filtrate and the washing liquid are adjusted to pH 5-6with trifluoroacetic acid, filtered and concentrated using a rotaryevaporator. For purification the residue is chromatographed on a silicagel column using ethyl acetate/n-hexane 4/1. Removal of the eluant byevaporation yields 14.42 g of the above sulfonamide in the form ofcolourless crystals which melt at 136°-138° C.

Example P3: Preparation of 3-(2-fluoroethoxy)-pyrid-2-ylsulfonamide(intermediate) ##STR24##

5.76 ml of 2-fluoroethanol are added dropwise, with cooling, to asuspension of 6.54 g of sodium hydride (55.6% NaH in oil) in 120 ml oftetrahydrofuran so that the temperature does not exceed 20° C. When thedropwise addition is complete, the reaction mixture is stirred at roomtemperature for 15 minutes and then a further solution of 10.56 g of3-fluoro-pyrid-2-ylsulfonamide in 60 ml of tetrahydrofuran is addeddropwise over a period of 10 minutes. The reaction solution is thenstirred for 10 minutes at room temperature and for 2 hours at refluxbefore it is cooled and concentrated. For purification, the oilremaining is chromatographed on a silica gel column using ethylacetate/hexane 4/1. Evaporation of the eluant yields a light-colouredoil which crystallises spontaneously, yielding 5.88 g of title productwhich melts at 122°-123° C.

Example P4: Preparation of 2-(2-isopropylthiopyrid-3-yloxy)-propionicacid methyl ester (intermediate) ##STR25##

12.3 ml of 2-bromopropionic acid methyl ester are added dropwise at roomtemperature to a mixture of 16.9 g of 2-isopropylthio-3-hydroxypyridineand 15.2 g of potassium carbonate in 250 ml of dimethylformamide and thebatch is stirred for 75 minutes. The suspension is introduced into amixture of ice-water (300 ml), 50 ml of 2N hydrochloric acid and 300 mlof ethyl acetate, washed four times with 120 ml of water and 120 ml ofethyl acetate each time, and the organic phase is dried over sodiumsulfate and concentrated by evaporation. 25.4 g of the desiredintermediate are obtained in the form of a viscous oil.

Example P5: Preparation of 2-(2-isopropylthio-pyrid-3-yloxy)-propan-1-ol(intermediate) ##STR26##

7.66 g of 2-(2-isopropylthiopyrid-3-yloxy)-propionic acid methyl esterin 40 ml of ether are added dropwise at 0°-6° C., over a period of 20minutes, to a mixture of 0.854 g of lithium aluminum hydride in 15 ml ofabsolute diethyl ether, and the mixture is then stirred for one hour at0° C. At 0° C. 0.85 ml of water, 0.85 ml of 30% sodium hydroxidesolution and 2.56 ml of water are slowly added in succession to theresulting suspension, which is then stirred for one hour at roomtemperature to complete the reaction. The reaction solution is filtered,washed with ether and concentrated by evaporation. 6.56 g of the desiredpyridyloxypropanol are obtained in the form of a colourless oil.

Example P6: Preparation of2-isopropylthio-3-(1-fluoropropan-2-yloxy)-pyridine (intermediate)##STR27##

1.13 g of 2-(2-isopropythiopyrid-3-yloxy)-propan-1-ol in 5 ml ofchlorobenzene are added dropwise at -40° C., over a period of 10minutes, to a solution of 0.89 g of diethylaminosulfur trifluoride(DAST) in 10 ml of absolute chlorobenzene. The reaction mixture isstirred for 3 hours at -30° C. and overnight at room temperature. Thereaction mixture is poured onto ice-water/ethyl acetate, adjusted to pH6-7 with saturated sodium hydrogen carbonate solution, and washed twicewith water and ethyl acetate each time. The organic phase is dried oversodium sulfate and concentrated by evaporation. Purification of thereaction mixture by silica gel chromatography using ethylacetate/n-hexane 1/8 as eluant yields 0.22 g of the desired fluorinederivative in the form of a light-yellow oil.

Example P7: Preparation of3-(1-fluoropropan-2-yloxy)-pyrid-2-ylsulfonamide (intermediate)##STR28##

4.31 g of gaseous chlorine are introduced over a period of 10 minutes,at -5° C., into a mixture of 3.5 g of2-isopropylthio-3-(1-fluoropropan-2-yloxy)-pyridine, 40 ml ofdichloromethane and 45.6 ml of 1N hydrochloric acid. The mixture is thenstirred for 15 minutes at -3° C. and, at that same temperature, nitrogenis introduced for a period of 20 minutes. The phases are washed threetimes with ice-water and dichloromethane each time and dried over sodiumsulfate. This dichloromethane solution is then added dropwise over aperiod of 10 minutes, at -50° C. to -40° C., to a mixture of 3.88 g ofammonia in 15 ml of dichloromethane, and the resulting mixture isstirred for 3 hours at room temperature and subsequently filtered. Thereaction solution is concentrated by evaporation, the oily residue istriturated with diethyl ether, and the crystal mass is filtered anddried. 3.2 g of the desired sulfonamide having a melting point of104°-106° C. are obtained.

Example P8: Preparation of2-isopropylthio-3-(cyclohexanon-2-yloxy)-pyridine (intermediate)##STR29##

7.29 g of 2-chlorocyclohexanone are added at room temperature to amixture of 8.4 g of 2-isopropylthio-3-hydroxypyridine and 7.6 g ofpotassium carbonate in 120 ml of dimethylformamide, and the mixture isstirred for one hour at 45°-50° C. After the addition of 1.46 g of2-chlorocyclohexanone and 1.52 g of potassium carbonate and after 2hours of a further analogous addition of 0.73 g of 2-chlorocyclohexanoneand 0.76 g of potassium carbonate, the suspension is stirred for afurther 3.5 hours at 45°-50° C. The resulting reaction solution ispoured onto a mixture consisting of 200 ml of ice-water, 50 ml of 2Nacetic acid and 100 ml of ethyl acetate, washed three times with 300 mlof ethyl acetate and 100 ml of saturated sodium chloride solution eachtime, dried over sodium sulfate and concentrated by evaporation. Theresidue is triturated with petroleum ether and filtered. 9.57 g of thedesired ketone having a melting point of 106°-110° C. are obtained.

Example P9: Preparation of2-isopropylthio-3-(1-hydroxycyclohexan-2-yloxy)-pyridine (intermediate)##STR30##

15.4 g of 2-isopropylthio-3-(cyclohexanon-2-yloxy)-pyridine in 100 ml ofether and 40 ml of dichloromethane are added dropwise at 0°-4° C., overa period of 10 minutes, to a mixture of 1.08 g of lithium aluminiumhydride in 135 ml of absolute diethyl ether, and the mixture is stirredfor one hour at 0°-4° C. There are slowly added dropwise in successionto that suspension, at 0° C., 1.61 ml of water, 1.61 ml of 30% sodiumhydroxide solution and 4.69 ml of water, and the mixture is tirred atroom temperature for one hour to complete the reaction. The reactionsolution is filtered, washed with dichloromethane and concentrated byevaporation. 14.47 g of the desired pyridyloxycyclohexanol are obtainedin the form of a yellow oil.

Example P10: Preparation of2-isopropylthio-3-(1-chlorocyclohexan-2-yloxy)-pyridine (intermediate)##STR31##

4.0 g of triphenylphosphine are added to a mixture of 3.21 g of2-isopropylthio-3-(1-hydroxycyclohexan-2-yloxy)-pyridine and 35 ml ofabsolute carbon tetrachloride and the mixture is stirred for 5 hours atreflux temperature. The resulting reaction mixture is stirred into amixture of 20 ml of dichloromethane and 20 ml of ice-water, and washedthree times with dichloromethane and water each time, and the organicphase is dried over sodium sulfate and concentrated by evaporation.Purification of the wax-like residue is carried out by way of a silicagel column with ethyl acetate/n-hexane 1/19 as eluant. 0.79 g of thedesired chloride is obtained in the form of a yellow oil.

Example P 11: Preparation of3-(1-chlorocyclohexan-2-yloxy)pyrid-2-ylsulfonamide (intermediate)##STR32##

1.33 g of chlorine gas is introduced for a period of 5 minutes at -5° to0° C. into a mixture of 1.35 g of 2-isopropylthio-3-(1-chlorocyclohexan-2-yloxy)-pyridine, 10 ml of dichloromethane and 14.1ml of 1N hydrochloric acid. The mixture is stirred at -5° to 0° C. for15 minutes and, at that same temperature, nitrogen is introduced for aperiod of 20 minutes. The phases are washed three times with ice-waterand dichloromethane each time and dried over sodium sulfate. Thisreaction solution is then added dropwise at -50° C. to -40° C., over aperiod of 10 minutes, to a mixture of 2.7 g of ammonia in 10 ml ofdichloromethane. The resulting reaction mixture is allowed to warm toroom temperature over a period of 2 hours, filtered and the filtrate isconcentrated by evaporation. 2.47 g of the desired sulfonamide having amelting point of 104°-106° C. are obtained.

Example P 12: Preparation ofN-[3-(2-chloroethoxy)-pyrid-2-yl-sulfonyl]-N'-(4,6-dimethoxypyrimidin-2-yl)urea##STR33##

4.52 g of N-(4,6-dimethoxy-pyrimidin-2-yl)phenyl carbamate, followed by2.46 ml of 1,5-diazabicyclo[5.4.0]undec-5-ene are added to a solution of3.55 g of 3-(2-chloroethoxy)-pyrid-2-ylsulfonamide in 45 ml ofacetonitrile. The reaction mixture is stirred at room temperature for 2hours and then concentrated using a rotary evaporator. The oil whichremains is triturated in a mixture of 10 ml of 2N hydrochloric acid and20 ml of water. White crystals are formed, which are filtered off withsuction and washed with water and ether. 4.52 g of title product, whichmelts at 156°-158° C., are obtained.

The compounds and intermediates listed in Tables 1 and 2 are obtained inan analogous manner to the above Examples:

                                      TABLE 1                                     __________________________________________________________________________     ##STR34##                           (I)                                      No.                                                                              R.sub.a                                                                         R.sub.1                                                                         R.sub.2                                                                          R.sub.3                                                                          R.sub.4                                                                          R.sub.5                                                                            R.sub.b                                                                         X      Y    E                                          __________________________________________________________________________    1.01                                                                             H H H  CH.sub.3                                                                         Cl CH.sub.2 Cl                                                                        H OCHF.sub.2                                                                           OCHF.sub.2                                                                         CH                                         1.02                                                                             H H H  CH.sub.3                                                                         Cl CH.sub.2 Cl                                                                        H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.03                                                                             H H H  H  H  Cl   H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.04                                                                             H H H  H  H  Cl   H OCH.sub.3                                                                            Cl   CH                                         1.05                                                                             H H H  H  H  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.06                                                                             H H H  H  H  Cl   H OCHF.sub.2                                                                           CH.sub.3                                                                           CH                                         1.07                                                                             H H H  H  H  F    H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.08                                                                             H H H  H  H  F    H OCH.sub.3                                                                            Cl   CH                                         1.09                                                                             H H H  H  H  F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.10                                                                             H H H  H  H  F    H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.11                                                                             H H CH.sub.3                                                                         H  H  F    H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.12                                                                             H H CH.sub.3                                                                         H  H  F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.13                                                                             H H CH.sub.3                                                                         H  H  F    H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.14                                                                             H H CH.sub.3                                                                         H  H  F    H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.15                                                                             H H CH.sub.3                                                                         H  H  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.16                                                                             H H CH.sub.3                                                                         H  H  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.17                                                                             H H CH.sub.3                                                                         H  H  Cl   H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.18                                                                             H H H  H  CH.sub.3                                                                         Cl   H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.19                                                                             H H H  H  CH.sub.3                                                                         Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.20                                                                             H H H  H  CH.sub.3                                                                         Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.21                                                                             H H H  H  CH.sub.3                                                                         Cl   H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.22                                                                             H H H  H  CH.sub.3                                                                         F    H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.23                                                                             H H H  H  CH.sub.3                                                                         F    H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.24                                                                             H H H  H  CH.sub.3                                                                         F    H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.25                                                                             H H H  F  F  F    H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.26                                                                             H H H  F  F  F    H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.27                                                                             H H H  F  F  F    H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.28                                                                             H H H  H  F  F    H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.29                                                                             H H H  H  F  F    H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.30                                                                             H H H  H  F  F    H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.31                                                                             H F F  H  F  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.32                                                                             H F F  H  F  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.33                                                                             H F F  H  F  Cl   H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.34                                                                             H F F  H  F  H    H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.35                                                                             H F F  H  F  H    H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.36                                                                             H F F  H  F  H    H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.37                                                                             H F F  H  F  CF.sub.3                                                                           H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.38                                                                             H F F  H  F  CF.sub.3                                                                           H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.39                                                                             H F F  H  F  CF.sub.3                                                                           H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.40                                                                             H H H  F  F  F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.41                                                                             H H H  H  F  F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.42                                                                             H F F  H  F  Cl   H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.43                                                                             H F F  H  F  CF.sub.3                                                                           H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.44                                                                             H H H  H  CH.sub.3                                                                         F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.45                                                                             H H H  H  H  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.46                                                                             H H H  H  H  Cl   H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.47                                                                             H H H  H  C.sub.2 H.sub.5                                                                  F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.48                                                                             H H H  H  H  Cl   H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.49                                                                             H H H  H  H  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.50                                                                             H H H  F  F  F    H OCH.sub.3                                                                            Cl   CH                                         1.51                                                                             H H H  F  F  F    H OCH.sub.2 CF.sub.3                                                                   N(CH.sub.3).sub.2                                                                  N                                          1.52                                                                             H H H  F  F  F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.53                                                                             H H CH.sub.3                                                                         H  CH.sub.3                                                                         Cl   H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.54                                                                             H H H  H  CH.sub.3                                                                         Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.55                                                                             H H C.sub.2 H.sub.5                                                                  H  H  Cl   H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.56                                                                             H H C.sub.2 H.sub.5                                                                  H  H  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.57                                                                             H H C.sub.2 H.sub.5                                                                  H  H  Cl   H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.58                                                                             H H CH.sub.3                                                                         H  H  Cl   H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.59                                                                             H H H  H  C.sub.2 H.sub.5                                                                  Cl   H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.60                                                                             H H H  H  C.sub.2 H.sub.5                                                                  Cl   H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.61                                                                             H H H  F  F  F    H OC.sub.2 H.sub.5                                                                      ##STR35##                                                                         N                                          1.62                                                                             H H H  F  F  F    H OCH.sub.3                                                                            CH.sub.3                                                                           N                                          1.63                                                                             H H H  F  F  F    H OCH.sub.2 CH.sub.3                                                                   NHCH.sub.3                                                                         N                                          1.64                                                                             H H H  F  F  F    H CH.sub.3                                                                             CH.sub.3                                                                           CH                                         1.65                                                                             H H H  F  F  F    H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.66                                                                             H H H  F  H  Cl   H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.67                                                                             H H H  F  H  CH.sub.2 Cl                                                                        H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.68                                                                             H H H  F  F  F    H OCH.sub.3                                                                            NHCH.sub.3                                                                         CH                                         1.69                                                                             H H H  Cl H  CH.sub.2 Cl                                                                        H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.70                                                                             H H H  Cl H  CH.sub.2 Cl                                                                        H OCH.sub.3                                                                            CH.sub.3                                                                           CH                                         1.71                                                                             H H H  F  F  F    H OCH.sub.3                                                                             ##STR36##                                                                         CH                                         1.72                                                                             H H H  H  H  CH.sub.2 Cl                                                                        H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.73                                                                             H H C.sub.2 H.sub.5                                                                  H  H  F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.74                                                                             H H CH.sub.3                                                                         H  CH.sub.3                                                                         F    H OCH.sub.3                                                                            OCH.sub.3                                                                          CH                                         1.75                                                                              ##STR37##                                                                 1.76                                                                              ##STR38##                                                                 __________________________________________________________________________

The melting points (m.p.) for the following compounds listed in Table 1are given in the following:

    ______________________________________                                        Compound No.                                                                             M.p.       Compound No. M.p.                                       ______________________________________                                        1.01       127-128° C.                                                                       1.24         142-144° C.                         1.02       134-135° C.                                                                       1.44         140-142° C.                         1.03       158-160° C.                                                                       1.45         134-136° C.                         1.04       133-136° C.                                                                       1.46         154-156° C.                         1.05       128-130° C.                                                                       1.47         126-128° C.                         1.06       138-140° C.                                                                       1.51         160-162° C.                         1.07       133-135° C.                                                                       1.52          94-96° C.                          1.08       158-160° C.                                                                       1.53         131-133° C.                         1.09       163-167° C.                                                                       1.54         130-132° C.                         1.12       118-120° C.                                                                       1.55         143-145° C.                         1.15       135-137° C.                                                                       1.58         144-147° C.                         1.16       121-123° C.                                                                       1.59         144-146° C.                         1.17       148-150° C.                                                                       1.60          99-101° C.                         1.18       138-140° C.                                                                       1.61         150-152° C.                         1.20       142-144° C.                                                                       1.62         153-155° C.                         1.22       139-141° C.                                                                       1.64         143-145° C.                         1.23       122-124° C.                                                                       1.65         150-152° C.                                               1.66         152-155° C.                                               1.67         156-158° C.                                               1.68         167-170° C.                                               1.69         126-128° C.                                               1.70         112-115° C.                                               1.71         160-163° C.                                               1.72         138-140° C.                                               1.73         142-144° C.                                               1.74         151-153° C.                                               1.75         152-155° C.                                               1.76         167-169° C.                         ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        (intermediates)                                                                ##STR39##                    (II)                                            No.  R.sub.a                                                                              R.sub.1                                                                             R.sub.2                                                                             R.sub.3                                                                            R.sub.4                                                                             R.sub.5                                                                             M.p.                                 ______________________________________                                        2.1  H      H     H     CH.sub.3                                                                           Cl    CH.sub.2 Cl                                2.2  H      H     H     H    H     Cl    136-138° C.                   2.3  H      H     H     H    H     F     122-123° C.                   2.4  H      H     CH.sub.3                                                                            H    H     F     104-106° C.                   2.5  H      H     CH.sub.3                                                                            H    H     Cl    94-96° C.                     2.6  H      H     CH.sub.3                                                                            H    CH.sub.3                                                                            Cl    oil                                  2.7  H      H     CH.sub.3                                                                            H    CH.sub.3                                                                            F                                          2.8  H      H     CH.sub.3                                                                            F    F     F                                          2.9  H      H     CH.sub.3                                                                            H    F     F                                          2.10 H      F     F     H    F     Cl                                         2.11 H      F     F     H    F     H                                          2.12 H      F     F     H    F     CF.sub.3                                   2.13 H      H     H     H    CH.sub.3                                                                            Cl    122-123° C.                   2.14 H      H     H     H    CH.sub.3                                                                            F     116-117° C.                   2.15 H      H     H     H    C.sub.2 H.sub.5                                                                     F     81-82° C.                     2.16 H      H     H     F    F     F     136-138° C.                   2.17 H      H     C.sub.2 H.sub.5                                                                     H    H     Cl    107-109° C.                   2.18 H      H     H     H    C.sub.2 H.sub.5                                                                     Cl    122-124° C.                   2.19 H      H     H     F    H     Cl    127-130° C.                   2.20 H      H     H     F    H     CH.sub.2 Cl                                                                         107-109° C.                   2.21 H      H     H     h    h     CH.sub.2 Cl                                                                         136-137° C.                   2.22 H      H     C.sub.2 H.sub.5                                                                     H    H     F     77-79° C.                     2.23 H      H     CH.sub.3                                                                            H    CH.sub.3                                                                            F                                          2.24                                                                                ##STR40##              150-151° C.                               2.25                                                                                ##STR41##              119-121° C.                               ______________________________________                                    

Biological Examples Example B 1: Pre-emergence Herbicidal Action onPlants

Plastics pots are filled with expanded vermiculite (density 0.135 g/cm³,water adsorption capacity 565 g/l). After saturating the non-adsorptivevermiculite with an aqueous emulsion of test compound in deionised waterthat contains the test compounds in a concentration of 70.8 ppm, seedsof the following plants are sown on the surface: Nasturtium officinalis,Agrostis tenuis, Stellaria media and Digitaria sanguinalis. The testcontainers are then kept in a climatic chamber at a temperature of 20°C., an illumination of approximately 20 klux and a relative humidity of70%. During a germination phase of 4 to 5 days, the pots are coveredwith transparent material in order to increase the local humidity, andwatered with deionised water. After the 5th day, 0.5% of a customarycommercial liquid fertilizer is added to the water. 12 days aftersowing, the test is evaluated and the action on the test plants isassessed in accordance with the following scale:

1: plants have not germinated or have died.

2-3: very pronounced phytotoxic action

4-6: medium action

7-8: weak action

9: no action, the plants grow like untreated control plants.

The tested compounds of Table 1 exhibit a strong herbicidal action inthis test.

Example B2: Post-emergence herbicidal action (contact herbicide)

A number of weeds, both monocotyledonous and dicotyledonous, are sprayedpost-emergence (at the 4- to 6-leaf stage) with an aqueous activeingredient dispersion at a rate of 8-500 g of test compound per hectareand kept at 24°-26° C. and 45-60% relative humidity. Three weeks later,the test is evaluated and the herbicidal action is assessed according toa scale of nine ratings (1=complete destruction, 9=no action) incomparison with an untreated control group. Ratings of 6 to 9(especially 7 to 9) indicate a good tolerance (especially in the case ofcultivated plants). The tested compounds of Table 1 exhibit a strong;herbicidal action in this test.

Example B3: Herbicidal action in wild rice (paddy)

The weeds Echinochloa crus-galli and Monochoria vag., which occur inwater, are sown in plastics beakers (surface: 60 cm² ; volume: 500 ml).After sowing, the beakers are filled with water up to the surface of thesoil. 3 days after sowing, the water level is increased to slightlyabove the soil surface (3-5 mm). Application is effected 3 days aftersowing by spraying the beakers with the test compounds. The rate ofapplication corresponds to a concentration of 8-500 g of activeingredient per hectare. The beakers are then kept in the greenhouseunder optimum growth conditions for rice weeds, i.e. at 25°-30° C. andat high humidity. The evaluation of the tests takes place 3 weeks afterapplication. The tested compounds of Table 1 damage the rice weedsduring this time.

What is claimed is:
 1. A compound of formula II ##STR42## wherein R₁ ishydrogen or fluorine;or R₁ together with R₃ is a C₂ -C₄ alkylene chain;R₃ is hydrogen, fluorine or C₁ -C₃ alkyl; R₂ is hydrogen, fluorine or C₁-C₃ alkyl; R₄ is hydrogen, fluorine, chlorine or C₁ -C₃ alkyl; R₅ ishydrogen, fluorine, chlorine, C₁ -C₃ alkyl, or C₁ -C₃ alkyl substitutedby fluorine or chlorine; and R_(a) is hydrogen or halogen, or a C₁ -C₄alkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio radical each of which may beunsubstituted or mono-or poly-substituted by halogen; with the provisothat at least one of the radicals R₁ to R₅ is fluorine, or one of theradicals R₄ and R₅ is chlorine.
 2. A compound according to claim 1,wherein R₁ and R₃, each independently of the other, are hydrogen orfluorine; R₄ is hydrogen, fluorine or chlorine; and R₅ is hydrogen orfluorine, or C₁ -C₃ alkyl that is unsubstituted or substituted byfluorine or chlorine.
 3. A compound according to claim 1, wherein R_(a)is hydrogen.
 4. A compound according to claim 1, wherein the radical ofthe formula Ia ##STR43## contains a maximum of 3 carbon atoms.
 5. Acompound according to claim 1, wherein in the radical of the formula Ia##STR44## at least one of the radicals R₃, R₄ and R₅ contains a halogenatom indicated for that radical.
 6. A compound according to claim 5,wherein only one of the radicals R₃, R₄ and R₅ is halogen.
 7. A compoundaccording to claim 1, wherein R₁ is hydrogen or fluorine; R₂ ishydrogen, fluorine, methyl or ethyl; R₃ is hydrogen, fluorine or methyl,or R₁ together with R₃ forms a C₄ alkylene chain; R₄ is hydrogen,fluorine, chlorine, methyl or ethyl; R₅ is hydrogen, fluorine, chlorine,trifluoromethyl or dichloromethyl; and R_(a) is hydrogen.
 8. A compoundaccording to claim 1, wherein said compound has the formula ##STR45## 9.A compound according to claim 1, wherein said compound has the formula##STR46##
 10. A compound according to claim 1, wherein said compound hasthe formula ##STR47##
 11. A compound according to claim 1, wherein saidcompound has the formula ##STR48##